Composition of matter and methods and steps of making and using the same



Patented Aug. 24, 1943 AND STEES OF SAD IE MAKING AND USING THE Mortimer Harvey, East OranggN; .l't, assignor to The Harvel-Gorporation; a corporation of "New Jersey Nc lirawing. ApplicationM'ay 13, 1939,

Serial No. 273,415

8: Claims." (01. 260-19) 7 The presentinvention relates generally tofriction; elements of the class of brake and clutch facings and the presentiinventionrelatesmore particularly to brake and clutch facings in which polymerizing; :and fatty'oils areblended. with phenol-aldehyde condensation reaction products which latter, in. their intermediate statesof cc-ndensation,are either soluble or intimately disper sible in said fatty oils andv in which brake and clutch .faci'ngs. the blend has been cured by heating to carry on the phenolraldehyde condensation reaction beyondthe intermediate states and to polymerize or dry the fatty oil to produce dry, oil resistant products having friction charactristics aclvantageousto brake and clutch facings, and having other advantageous characteristics. such as infusibility at certain jhigh temperatures and uniformity. of frictional characteristics at'high temperatures and under extreme changes oftemperature and into which said brake and clutch facings said dry, oil-resistant products are incore porated in the comminuted form. Generally stated, the'present invention relates to theformation of a friction producing material made with anoilfsoluble 'phenolresin and a glyceride oil broughttoagstage of cure which can be ground to-a granular size, or otherwise comminuted, and can be. added to other ingredients commonly used in mixtures for forming brake linings and clutch facings, such as asbestos, rubber, carbon and so on. f

In the practice of the present invention phenols are-use'd which; upon condensation with areactive methylene-group supplying material, will produce a condensation "product of resinous character which is soluble or intimately dispersible'in fatty oils of polymerizing and drying character. 'The phenol and the reactive methylene group supply ing material can be condensed first to an intermediate stat and then tblended 'with :the fatty oil by dissolving or intimately dispersing and'further condensed toa finalstateor curing with heat during which. curing the fatty. oil component of the blend is polymerized or dried whereby the entire blend becomes dryand; resistant to. the solvent action of oils and isain'a; state suitable for being comminuted by shredding, bygrinding or by some other. method. i 1

Examples of the fatty oils suitable foruse in the practice of the present invention are linseed oil, China-wood oil and soy beanoil and artificial oils made as by separatingthe glyceride radicles and fatty acids radicles of fatty oils-and recombining these radicles to formotherfatty oils. Th fatty oils suitable for use in the practiceof the present inventionjare called herein, fatty oils which-can be polymerizedor dried. i j V Examples of the reactive methylene group-supplying material suitable for use in the practice of the present invention are formaldehyde, paraformaldehyde, paraldehyde, hexamet'hylene tetramine, acetaldehyde and, furfulaldhyde. v

Examples of phenols which upon condensation with a reactive methylene group, form condensation products soluble or intimately dispersible or miscible with fatty oils, are the tertiary alkyl phenols, e. g para tertiary butyl phenol, para tertiary amyl phenol, the'two para tertiaiy hexyl phenols, para phenyl' phenol, the ortho phenols corresponding to those phenolsabove' mentioned, carvacrol, xylenols; para cresol, mixtures of para cresolwit'h ortho'cresol' and metacresoland commercial phenols and mixtures of phenols which upon condensation with a reactivemethylene group give oil soluble condensation product, cashew-nut shell liquid," marking nut shellliq'uid, Japanese lac, and their several characteristic phenolic components and derivatives such as anacard-ic acid, cardol, anacar'dol, "urushiol, cardanol and other similarphenolsifound in or derived from. the plants of the'hnacardiacea'e family, and phenols generally which-have unsaturated hydrocarbon side-chains and which,with a reactive methylene group, ive condensation products soluble in or dispersible with fatty oils and. curable therewith to a dry, oil resistant form which can-be produced in a final comminutecl form. Thephenols: suitabl for the practice of the presentinvention are'classedherein as those phenols which haveat least one of the readily reactive positions (ortho and para) unoccupied and which have a hydrocarbon substituent or substituents on the nucleus which give thephenolthe characteristics of being soluble in oils and offorming aldehyde condensation products soluble or dispersi-ble in oils and particularly in fattyoils of the kind described above Otherphenolssuitable for use in the practice of the present invention have at least two of the readily reactive .positions (ortho and para positions) unoccupied and some have al1 three of the readily reactive positions (the para and both of the ortho positions) unoccupied. i

The characteristics of heat resistance, heat conductivity, non-softening. under heat and resistance. to water, oil and chemicals and especially uniformity of frictional characteristics. over a widerange of temperature make, the variousprodnets of cashew nut shell liquid suitable for usein friction elements. Also, the characteristic which terials, for example those having a methylene 3 group such as formaldehyde and paraform, are advantageous for the handling and preparation of the intermediate and final products.

Other materials can be used with the modified cashew nut shell liquid and can be added before or after the modification process and also can be produced simultaneously with the modification such for example as in the case of producing a and polymerizing and drying fatty oils of the.

present invention are given below.

Example A of the weight of the cashew nut shell liquid of the cashew nut shell liquid. The heating of this phenol-formaldehyde reaction product simu1- salts can be separated from the treated cashew taneously with the production of a cashew nut shell liquid formaldehyde reaction product such as is disclosed in Patent Number 1,725,797. Drying oils, natural and artificial resins, gums, pitches, waxes, rubber, thepolyhydricfalcoholpolybasic acid'type of resins, cellulose esters, sulphur, and so on can also be used with the modi-' fied cashew nut shellliquid or to produce the modification of the cashew nut shell liquid with or without the aid of heat, and with or without increase or decreasein pressurei Also ethers, esters, hydrogenation products, and so on of cashew nut shell liquid can be used. Another form of modified cashew nut shell liquid suitable for the purposes of the present invention is produced from the decarboxylated product called cardanol which can be obtained by distilling cashew nut shell liquid preferably at a low pressure (about 10 millimetersof mercury) or bydistilling with steam to removethe carbon and oxygen atoms of the carboxyl group of the anacardic acid ingredients of the cashew nut shell liquid and to separate other ingredients. Card.- anol can be modified to the dry, infusible state in a number'of ways such as those described above for cashew nut shell liquid itself. Further," numerous combinations 'of the methods disclosed and referred to above can be used to modifycashew 'nut shell liquid and derivatives thereof to'a dry, infusible state to produce various materials suitablefor the various purposesof the present invention and tosuitthe various conditionsunder which friction elements are used, Also the residue obtained by distilling cashew nut shell liquid, as with steam or under vacuum, to obtain cardanol is suitable as a phenol for the practice of the present invention. This residue can be, for example, from forty per cent to sixty .per cent, more or less, of the cashew nut shell liquid subjected to distillation. In ome cases this residue is used as obtained, in

other cases this cashew nut shellliquid residue is .1

polymerized before or during the process of practicising the method of the present invention. [The present application is a continuation in part of my copending application Serial Number 46,743, filed October 25, 1935, issued to Patent Number*2,165,l40, July 4, 1939, and of all that part of said copending application which describes or refers to the use of oil soluble phenolaldehyde (reactive methylenegroup) condensation productswith polymerizing anddrying fatty oils toobtain dry, oil resistant brake linings and clutch facings.

Illustrative examples of mixtures of friction materials containing the blends of oil solible phenol-aldehyde condensation products or resins a tween 450 F. to 550 F. in the manner of 'pre' paring a Varnish to get-a. body. This heating water, with rapid stirring to disperse the sulphuric acid thoroughly and quickly throughout mixture is carried to about 300 F. to about 350 F. Up to this point the material is a thick liquid polymer and is identified herein as material of Example A. During this process certain metals which occur naturally in cashew nut shell liquid are precipitated as sulphate salts and these Example B s (a) To onemole of para tertiary 'butyl phenol,

about two moles'of formaldehyde (in about 40%. solution in water) are added, with a sodium hydroxide solution as a catalyst, and left to stand for about five days at room temperature/after which the mixture is neutralized and the resin. isdehydrated. To one part by weight of this resin, abouttwo partsv by weight of China-wood oil are added and the mixture heated up to be-.

is continued until the body is quite heavy but still pourable at temperatures convenient for handling. The heavy-bodied resin-China-wood oil mixture is then poured, while hot, into shallow pans to a depth of about three or four; inches and cured in an oven at about 325 0.,for about sixteen hours. The resin-China-woodoil product,-when cool, is solid but just slightly resilient and can be shredded or comminutedinto small particles. I r r v (2)) Instead of two parts by weightofChinawood oil to one of the resin above, 'onepart-of China-wood oil is added and the mixture bodied and cured in a manner substantially the same as set forth above. This resin-China-wood 011 product is solid and somewhat brittle and can be comminuted to fine particles.

(c) The proportion of resin to. China-wood oil can be varied between and outside of the limits bounded by the ratios "set forth inExampleB (a) and (b) to obtain final comminuted prod ucts of various consistencies. Also to varythe desired consistency the temperatures and 'duration of bodying and curing can be varied. And

also to obtain various consistencies linseed oilo'r if cold, heated to about 300F. to makeitflow above, obtain a rhard, brittle able, is strained through ascreen to-iremove any lumps 01:- solid' particles and at -about 200. I. mixed witlione hundred parts of :Chinaawood oil, and with 'about: ten part of diethyl sulphate andabouttwo and one-halfi parts of furfuralde- 'hyde, the mixture being thoroughly. stirredand poured into shallow pans and cured "for, about when cold is comminutedto small particles. The

. quantity of furfur aldehyde can be increased to Example E bo t qua parts'rhy weijehtlo .cardanol, ph n01 carbolicacid). and,a3 7.% solution of formal.- l hyd ar heated iiha mQ ia as a catalyst, under a refluxcondenseif for about, one hour, after which theresultingresin isseparated from the water while hot, and dehydrated. Aboutfou herbs i isiresin; e g t art f -Qdiedlin d oil, forty-eight parts of cashew, nutshell liquid residue,..one partof diethyl sulphate and'three parts of furfuraldehyde are melted together, by first heating the resin, bodied linseed oil and cashew nut shell liquid residue at about 260.Ff

to about 300. F. and then adding the diethyl sulphate and furfuraldehyde at about 180 F., and thoroughly intermixed, after which the mixture is cured in shallow pans at'about 275 F. for about sixteen hours. The cured material is comminuted or pulverized.

The cardanol of this last example and methods of producing it are described in my Patent Number 2,098,824, issued November 9, 1937.

General example.

A general illustrative example of a brake lining or clutch facing composition made up of any of the comminuted phenolic resin-glyceride oil materials described above as illustrative examples or of any mixture of any two or more of them is as follows. form known in the brake lining manufacturing field as long fiber asbestos, from ten to fifteen parts of a binder, and from fifteen to ten parts of the selected comminuted phenolic resin-glyceride oil material are thoroughl intermixed, molded to shape and cured to modify the binder to a dry state. The binder can be rubber, a phenolic resin, a drying oil or any combination thereof, examples being well knownin the brake and clutch manufacturing field and in the patent art. Any of the phenolic resins described above as suitable for making the comminuted material of the present invention, when in an intermediate state of condensation, with or without a polymerizing or drying glyceride oil, can be used as the binder and. in addition to being a binder, will serve with the comminuted material and the asbestos as a frictional functioning part of the brake lining or clutch facing. For further illustrative examples of brake lining and clutch Seventy-five parts of asbestos, in the facing compositions: using the comminuted'mater rial ofthe-present invention, thatiis,,comminuted, dry material ma'de' fromlla blend 10f. a phenol-a1- denydaresinanda or polymerizing glyc- 1 eride oil, reference is iherebyimade to dis? closure inmy .c'opending application .Serial Number 37,749, f ledAugust 24, 1935,-toPatent Number 32,164,326, issuedduly: 19.39; of: which the presentapplicbtion is a. oontinuationrinlpart, and

particularly to the general and specific examples l. A composition of matterfcapable of aug mentingithe frictional characteristics of a friction el'ement, comprisinga substantially dry and infusible composition obtained by heat convert ing to a substantially dry and inf usible material, a mixture of a heatpolymeri-zable oil, a dialkyl sulphate, furfuraldehyde anda product selected from the group-consisting of cashew nut shell liquid and residue of cashew nut shell liquid obtained by distilling cashew nut shell l-iquid'unt'il the quantity by weight of the residueis between about 40 to60% of the quantity'byweight of said cashewnut shell liquid! 2'. A composition of matter, capable of augmenting the-frictional characteristics of a friction element,"cornprising a substantially dry-and infusible composition obtained by heatconverting-to a substantially dry and infusiblematerial, a mixture of a heat polymerizable oil, a dialkyl sulphate, furfuraldehyde and aproduct selected from the group consisting of cashew nut shell liquid and residue of cashew nut shell liquid obtained by distilling cashew nut shell liquid until thequantity by weight of the residue is between about 40 to 60% of the quantity by. weight of said cashew nut shell liquid, the quantity of said product being materially greater than that of said furfuraldehyde.

3. A composition of matter, capable of augmenting the frictional characteristics of a friction element, comprising a substantially dry and infusible composition obtained by heat converting to a substantially dry and infusible material, a mixture of a heat polymerizable oil, di-

ethyl sulphate, furfuraldehyde and a product selected from the group consisting of cashew nut shell liquid and residue of cashew nut shell liquid obtained by distilling cashew nut shell liquid until the quantity by weight of the residue is between about 40 to 60% of the quantity by weight of said cashew nut shell liquid.

4. A composition of matter, capable of augmenting the frictional characteristics of a friction element, comprising a substantially dry and infusible composition obtained by heat converting to a substantially dry and infusible material, a mixture of a heat polymerizable oil, diethyl sulphate, furfuraldehyde and a product selected from the group consistingof cashew nut shell liquid and residue of cashew nut shell liquid obtained by distilling cashew nut shell liquid until the quantity by weight of the residue is between about 40 to 60% of the quantity by weight of said cashew nut shell liquid, the quantity of said product being materially greater than that of said furfuraldehyde.

5. A composition of matter, capable of augmenting the frictional characteristics of africtionelement, comprising asubstantially dry and infusible composition obtained by heat converting to a substantially dry andinfusible'material, a mixture of diethyl'sulphate, furfuraldehyde, a heat polymerizable oil, and residue of cashew nut shell liquid'obtained by distilling cashew nut shell liquid until the quantity by weight of the residue is between about 40 to 60% Iof'the quantity by weight of said cashew nut shell liquid, the quantity by weight of said residue being greater than the quantity by Weight of eithersaid aforementioned other substances and the quantityv by weight of said oil being greater than the quantity by weight of either said first two mentioned substances. v V

6. A composition of matter, capable of augmenting the frictional characteristics of a trio tion element, comprising a'substantially dry and infusible composition obtained'by heat converting to a substantially dry and infusible material, a mixture of a heat polymerizable oil, diethyl sulphate, furiuraldehyde and residue of cashew nut shell liquid obtained by distilling cashew nut shell liquid until the quantity by weight of the residue is between about 40 to 60% of the quantity by weight of said cashew nut shell liquid, the ratio of the quantity by Weight ofsaid residue to the quantity by weight of said oil being about 4 to 1, the ratio of the quantity by weight of said oil to the quantity by weight of said diethyl sulphate being about to 1 and the quantity by Weight of said oil being greater than the quantity by weight of said furfuraldehyde.

7. A composition of matter, capable of augmenting the frictional: characteristics of -a .fri'cr vtion element, comprising a'substantiallydrygand infusible' composition obtained by heat converting to a substantially dryand infusible material, a mixture" of diethyl sulphate, *iurfuraldehyde,

China-Wood oil ;a'ndvresidue. of cashew nut-shell 1 liquid obtained by distilling" cashew nutshell liquiduntil'the quantity byweight of the residue isv between about to160% of thequantityby weight of said cashew nut shell liquid, the quail.-

, tity byweightofsaid residue being greaterv than the'quantity lay-weight of either said aforemenliquid until the quantityby weight of the residue is between/Mite of the quantity by weight of said cashew nut shell liquid, the ratio offlthe quantity by weight of said residue to the quantity by weight ofsaid oil 'being about 4 to l, the

ratio of the quantity by weight of "said oil tovthe quantity by weight of said diethyl sulphate being about .10 to land the quantity by weight of said oil being greater than the quantity by. weight of said furfuraldehyde.

MORTIMER T. 

